Fundamental ash deposition characteristics in pulverized coal reaction under high temperature conditions

Three types of coal with the different melting temperature and ash content were burned under the condition of high-temperature air pulverized coal reaction. A water-cooled tube was inserted into the furnace to make the ash adhere. Particle size and composition distributions of ash particles in both reacting coal particles and depositing layer were analyzed, using a Computer Controlled Scanning Electron Microscope, to study the deposition behaviors of ash particles. As a result, quantity of the ash deposition on the tube surface increases with a decrease of the melting temperature of coal ash. Index of fraction of the ash deposition depended on the coal type. For structure of the deposit layer, fine particles of size less than 3 μm mainly consisted of the initial layer for three types of coal, and the thickness was about 30 μm. Deposition of fine particulates of about 3 μm became a trigger of initial deposition at the stagnation point of tube even if irrespective of coal type is burned. The chemical compositions of ash particles in the reacting particles differed from those in the initial deposition layer. The deposition phenomenon relates to the particle size distribution of ash formed, the flow dynamics surrounding the probe, the chemical compositions in each ash particle and so forth.     

Influence of catalytic particle size on the performance of fluidized-bed chemical vapor deposition synthesis of carbon nanotubes

In this paper, the impacts of catalytic particle size on the overall reactor performance for carbon nanotubes (CNTs) production using a fluidized-bed chemical vapor deposition (FBCVD) process have been studied. Six different particle size fractions (10-20 μm, 20-53 μm, 53-75 μm, 75-100 μm, 100-200 μm, and 200-300 μm) were selected. It was observed that the smaller the catalytic particle diameter, the greater the carbon deposition efficiency and the greater CNT synthesis selectivity. The 10-20 μm catalytic particles exhibited 30% higher carbon deposition efficiency than the 200-300 μm catalytic particles. The selectivity toward CNTs formation was also approximately 100%. These observations could be explained by the fact that when the diameter of the catalytic particle gets smaller, the breakthrough capacities during frontal diffusion will be bigger due to a shorter diffusion path length within the particle. Moreover, the fine particles ensured high interstitial velocity which subsequently enhances the heat and mass transfer, and consequently improves the CVD reaction.     

Separability of hydrogen from hydrogen-carbon dioxide mixture across silica-silicalite-1 film

Colloidal silica particles, grown on a mesoporous silica layer using macroporous alumina substrate as a support, were used to separate hydrogen from carbon dioxide. The particles transformed into rectangular interlocking silicalite-1 structures with size approximately 8 × 4 × 4 μm, oriented epitaxially with film thickness of ca. 22 μm. The silicalite-1 particles grew in size due to the effect of structure directing agent (SDA), Oswald ripening and hydrothermal synthesis that promoted the growth of the colloidal particles into crystals. Permeation experiment using silicalite-1 showed that CO₂ flux decreased and H₂ flux increased with increase in temperature. The separability of H₂ that was unity at the lower temperature became increased in value as the temperature was raised.     

A comparison of the results obtained from grinding in a stirred media mill lignite coal samples treated with microwave and untreated samples

Various studies have been carried out on the effect of microwave-treatment on grinding different types of coal. However, the effect of microwave treatment on grinding coal samples −3.35 mm in size which can be considered to be fine is still under investigation. The purpose of this paper is to make contributions to these studies conducted. In the study, lignite coal samples with pyritic sulphur and 25% structural moisture were crushed below −3.35 mm particle size using jaw and cone crushers and then classified into three different mono size groups by Russel sieve. For a complete removal of the structural moisture from the lignite coal, a microwave application with 600 W needs approximately 35% more energy consumption than that with 850 W. The untreated coal samples and the ones treated with microwave at 850 W were ground for 5, 15, 30, 60, 120 s in a stirred media mill. The breakage rates of microwave-treated coal increased and accordingly the ground products of microwave-treated coal yielded finer particles than −106 μm as compared to untreated coals. The untreated and microwave-treated feed coals of −3350 μm and −1180 μm particle sizes were ground for 2 min in the stirred media mill. It was found that the increases in the rate of weight percentages for −106 μm particle size fraction after 2 min of grinding of untreated and microwave-treated feed coals of −3350 μm and −1180 μm were found to be 15.81% and 2.69%, respectively. Moreover, Hardgrove Index (HGI) test results of lignite coal showed that the HGI index value increased by approximately 23% after microwave treatment with 850 W.     

Spherical porous carbon particles derived from suspensions and sediments of resorcinol-formaldehyde particles

The goal of this study is the completion of the parameter field of resorcinol-formaldehyde solutions towards the regime of non-monolithic phases. For low sodium carbonate concentration and low mass content of resorcinol and formaldehyde in the starting solution the formation of spherical particles rather than monolithic gels is observed. The organic precursors were converted into carbon powders by pyrolysis. The resulting carbon particles were characterized by scanning electron microscopy (SEM), nitrogen sorption and small-angle X-ray scattering (SAXS). The study shows that carbonization of the organic particles results in spherical carbon particles with a micropore volume of about 0.28 cm³/g. The composition of the starting solution, however, strongly affects the external surface area as determined from sorption data for the organic as well as for the corresponding carbon particles; the values derived can be converted into average diameters of spherical particles ranging from 30 nm to 5 μm. Complementary SEM and SAXS measurements confirm these findings. A diameter of 5 μm appears to be the upper size limit in particle size forming, while 30 nm spheres develop near the formation of a continuous gel at relatively high sodium carbonate concentrations.     

Adsorption of lipopolysaccharide on carbon sieves

Adsorption of lipopolysaccharide, LPS, on carbon sieves Carboxen 1003 and Carboxen 1010 has been studied. LPS adsorption kinetics is initially faster on smaller size (1-10 μm) particles of predominantly microporous Carboxen 1010 compared to Carboxen 1003 (150-200 μm) particles. However, the adsorption capacity of micro/meso/macroporous Carboxen 1003 by LPS is higher than that of Carboxen 1010 since the former carbon has wider pores that can accommodate large lipopolysaccharide molecules or their agglomerates. Carboxen 1010 probably adsorbs LPS mainly on the external (macropore) surface.     

Formation of submicron poorly water-soluble drugs by rapid expansion of supercritical solution (RESS): Results for Naproxen

Numerous results of multitude investigations indicate that the particular properties of supercritical fluids can be conveniently exploited for the formation of submicron particles. In case of pharmaceutical substances the poor dissolution behaviour and therewith bioavailability of drugs in biological media can be enhanced dramatically by reduction of the particle size. In this paper we report the application of RESS (Rapid Expansion of Supercritical Solutions) and RESSAS (Rapid Expansion of Supercritical Solution into Aqueous Solution) to produce submicron particles of Naproxen, a poorly water-soluble drug. Thereby the effect of various process conditions on the obtained product properties was investigated. The experimental results show, that the RESS processing of Naproxen leads to particles in the range from 0.56 to 0.82 μm which is about 22 times smaller than the unprocessed powder. RESSAS experiments show, that stabilized Naproxen particles have an average diameter of 0.3 μm for drug concentrations up to 1 g/dm³ in 0.4 wt% PVP solution while expansion into a 0.4 wt% Tween^® 80 solution produced particles 8 μm in diameter. Furthermore, it is shown that the improved dissolution behaviour of the processed powder depends on the particle size and hence increased surface area and on the pH-value of the dissolution media.     

Mechanical activation of fly ash: Effect on reaction, structure and properties of resulting geopolymer

Geopolymerisation of mechanically activated fly ash was studied at ambient (27 °C) and elevated (60 °C) temperatures by isothermal conduction calorimeter. Under both the conditions, mechanical activation enhanced the rate and decreased time of reaction. It was interesting to observe that in the samples milled for 45 min (median size ∼5 μm), a broad peak corresponding to geopolymerisation initiated at 27 °C after 32 h. The rate maxima at 60 °C, a measure of fly ash reactivity, showed a non-linear dependence on particle size and increased rapidly when the median size was reduced to less than 5-7 μm. Improvement in strength properties is correlated with median particle size, and reactivity of fly ash. The characterisation of the geopolymer samples by SEM-EDS, XRD and FTIR revealed that mechanical activation leads to microstructure and structural variations which can be invoked to explain the variation in the properties.     

The effect of oxygen-to-fuel stoichiometry on coal ash fine-fragmentation mode formation mechanisms

Ash particles smaller than 2.5 μm in diameter generated during pulverized coal combustion are difficult to capture and may pose greater harm to the environment and human health than the discharge of larger particles. Recent research efforts on coal ash formation have revealed a middle fine-fragment mode centered around 2 μm. Formation of this middle or fine-fragment mode (FFM) is less well understood compared to larger coarse and smaller ultrafine ash. This study is part of an overall effort aimed at determining the key factors that impact the formation of FFM. This work examined the effects of oxygen-to-fuel stoichiometry (OFS).Pulverized Illinois #6 bituminous coal was combusted and the ash generated was size segregated in a Dekati low pressure inertial impactor. The mass of each fraction was measured and the ash was analyzed using scanning electron microscopy (SEM) and X-ray microanalysis. The FFM ash types were classified based on the SEM images to evaluate the significant fine-fragment ash formation mechanisms and determine any possible link between stoichiometry and formation mechanism.From the particle size distributions (PSDs), the coarse mode appears unaffected by the change in OFS, however, the OFS 1.05 lowered the fraction of ultrafine ash in relation to the higher OFS settings, and appears to increase the portion of the FFM. An intermediate minimum was found in the FFM at 1.3 μm for the 1.20 and 1.35 OFS tests but was not observed in the 1.05 OFS. SEM analysis also suggests that OFS may contribute to changing formation mechanisms.     

Size effect on mechanical properties of micron-sized PS-DVB polymer particles

A nanoindentation-based flat punch method has been developed to determine the stress-strain behaviour of single micron-sized Ugelstad polystyrene-co-divinylbenzene (PS-DVB) particles in compression. Five groups of particles with identical chemical compositions but different diameters have been tested. The diameter of the PS-DVB particles varied from 2.6 μm to 25.1 μm. Constant relative deformation rate has been applied with two maximum strain levels of 5% and 10%. Results show that the particle compressive stress-strain behaviour is strongly size-dependent. The smaller the particle size is, the stiffer the particle behaves. Analyses indicate that the pre-load and adhesion during the flat punch test play a minor role on the size effect. The presence of a core-shell structure can possibly be a main contribution to the size effect. Finite element analyses have been carried out to demonstrate this surface shell effect.     

Toughening of polypropylene with calcium carbonate particles

Polypropylene-CaCO₃ composites were prepared on a twin screw extruder with a particle content of 0-32 vol%. The influence of particle size (0.07-1.9 μm) and surface treatment of the particles (with and without stearic acid) on the toughening properties were studied. The matrix molecular weight of the polypropylene was also varied (MFI 0.3-24 dg/min). The experiments included tensile tests, notched Izod impact tests, differential scanning calorimetry (DSC), scanning electron microscopy and rheology experiments. The modulus of the composites increased, while the yield stress was lowered with filler content. This lowering of yield stress was connected to the debonding of the particles from the polypropylene matrix. From DSC experiments it was shown that the particle content had no influence on the melting temperature or crystallinity of the PP phase, also particle size showed no effect on the thermal properties. The impact resistance showed large improvement with particle content. The brittle-to-ductile transition was lowered from 90 to 40 °C with the addition of CaCO₃ particles. Notched Izod fracture energy was increased from 2 up to 40-50 kJ/m². The stearic acid coating on the particle surface showed a large positive effect on the impact strength. This was mainly due to the improved dispersion of the CaCO₃ particles. Aggregates of particles clearly had a detrimental effect on the impact behaviour of the composites. The smaller particle sizes (<0.7 μm) showed coarse morphologies and this lowered the toughening efficiency. The molecular weight of the polypropylene matrix had a profound effect on the toughening properties. A higher molecular mass shifted the brittle-to-ductile transition towards lower temperatures. At the higher filler loads (>20 vol%), however, still problems seem to occur with dispersion, lowering the toughening efficiency. Of all particle types used in this study the stearic acid treated particles of 0.7 μm were found to give the best combination of properties. From the study of the micro-toughening mechanism it was shown that at low strain the particles remain attached to the matrix polymer. At higher strain the particles debond and this leads to a change in stress state at the particle size level. This prevents crazing of the matrix polymer and allows extensive plastic deformation, resulting in large quantities of fracture energy.     

Investigation of turbulence modulation in solid–liquid suspensions using parallel competing reactions as probes for micro-mixing efficiency

The Bourne and the Villermaux competitive reaction chemistries were applied to study the effects of suspended particles on the yield of an undesired product and hence to infer their effects on local dissipation rates. Two-phase micro-mixing experiments were carried out in a 1 l stirred vessel, agitated by a pitched-blade turbine, using four particle size ranges: 70–100, 250–300, 700–750 and 1000 μm. Experiments were carried out with up to 1.75 vol% particles in the Bourne scheme and 3 vol% in the Villermaux scheme. Both reaction schemes gave qualitatively similar results, although stronger effects of added particles were obtained with the Bourne chemistry. The effect of 700–750 μm particles could not be distinguished from experimental error, but the other size ranges gave increased by-product yields and suppressed the dissipation rates. These results confirmed earlier two-phase PIV observations: smaller particles (70–100 and 250–300 μm) gave maximum suppression at ∼1 vol%. Above this volume fraction, the level of suppression decreased and in some cases turbulence augmentation occurred, indicating that particle concentration, as well as size, is an important factor.     

Mineralogy and microstructure of sintered lignite coal fly ash☆

Lignite coal fly ash from the ‘Nikola Tesla’ power plant in Yugoslavia has been characterised, milled, compacted and sintered to form monolithic ceramic materials. The effect of firing at temperatures between 1130 and 1190 °C on the density, water accessible porosity, mineralogy and microstructure of sintered samples is reported. This class C fly ash has an initial average particle size of 82 μm and contains siliceous glass together with the crystalline phases quartz, anorthite, gehlenite, hematite and mullite. Milling the ash to an average particle size of 5.6 μm, compacting and firing at 1170 °C for 1 h produces materials with densities similar to clay-based ceramics that exhibit low water absorption. Sintering reduces the amount of glass, quartz, gehlenite and anhydrite, but increases formation of anorthite, mullite, hematite and cristobalite. SEM confirms the formation of a dense ceramic at 1170 °C and indicates that pyroplastic effects cause pore formation and bloating at 1190 °C.     

Reactivities of Blair Athol and Nang Tong coals in relation to their behavior in PFBC boiler

The combustion reactivities of Blair Athol (BA) and Nang Tong (NT) coals were measured by thermogravimetry to understand their different behaviors in the PFBC boiler. The reactivity of BA was much the same as that of NT coal but their chars showed different characteristics. BA char of higher surface area (25 m²/g) showed slightly higher reactivity than that of NT char of smaller surface area (7 m²/g). BA coal showed heterogeneous ignition even at its particle size of as large as +355 μm while NT coal showed homogeneous ignition at the average particle size over 75 μm heterogenous one occurring with finer particle size (−75 μm). Higher calorific value of BA volatile matter and higher reactivity of its char than those of NT coal causes of its heterogeneous ignition with an intense DTA peak, which may lead to local heating at its combustion and to yield reactive CaO from limestones causing of bed materials agglomeration in the PFBC.     

Numerical simulation of microparticles penetration and gas dynamics in an axi-symmetric supersonic nozzle for genetic vaccination

This paper describes two phase (solid particles/gas) flow in a supersonic nozzle that is part of a device for micromolecular vaccine/drug delivery. It accelerates micro solid particles to high speeds sufficient to penetrate the viable epidermis layer to achieve the pharmaceutical effect. Helium is used as the driving gas for the solid particles because of its high compressibility factor. A numerical parametric study was performed for gas pressures ranging between 3 and 6 MPa and gold particles of diameters 1.8 μm and 5 μm. The computed results show that uniform particle velocity was achieved at standoff distance of 2 exit diameters (D_e) downstream of the device exit with particles concentrated on the supersonic core jet. Increasing the helium pressure from 3 to 6 MPa caused an increase in the particle velocity of 24% for particles with a diameter of 1.8 μm and 7% for particles of diameter 5 μm at the standoff distance. Furthermore increased gas pressure has adverse effect on particles concentration. As the inlet pressure increases, the particles are concentrated more at the core of the nozzle. Semi-empirical particle penetration calculation confirms the numerical results that the 5 μm particles penetration distance is 45-135 μm and the 1.8 μm diameter penetration is 35-95 μm beneath the skin. Comparison of different geometries has been done in order to understand each section function and to gain optimum performance.     

Coprecipitation of Cefuroxime Axetil-PVP composite microparticles by batch supercritical antisolvent process

Batch supercritical antisolvent precipitation (SAS) process was used to coprecipitate Cefuroxime Axetil amorphous (CFA, antibiotic) and Polyvinylpyrrolidone (PVP-K30) for preparing drug-polymer composite particles. Solutions of CFA and PVP-K30 in methanol with overall concentrations of 50-150 mg/ml and polymer/drug ratios of 1/1-4/1 were sprayed into the CO₂ at 70-200 bar and 35-50 °C with drug + polymer solution injection rates of 0.85 and 2.5 ml/min. Spherical particles having mean diameters of 1.88-3.97 μm, distribution ranges of 0.82-9.7 μm (the narrowest distribution) and 0.91-46.64 μm (the broadest distribution) were obtained. Mean particle size was not affected significantly with the change of process parameters. It was only affected by pressure change. On the other hand particle size distribution was affected by pressure, temperature, drug + polymer solution injection rate and concentration. It was observed that temperature and polymer/drug ratio affected the particle morphology most. The drug release rate of SAS-coprecipitated CFA-PVP (1/1) particles was almost 10 times slower than the drug alone. As the ratio of the polymer increased drug release rate also increased due to the wetting effect of PVP.     

Recrystallization of erlotinib hydrochloride and fulvestrant using supercritical antisolvent process

Recrystallization of two anti-cancer active pharmaceutical ingredients (APIs), erlotinib hydrochloride (erlotinib HCl) and fulvestrant, using supercritical antisolvent (SAS) process was investigated in this study. The most commonly used supercritical carbon dioxide was employed as the antisolvent. Effect of three process parameters including the operating temperature, pressure and solution flow rate have been studied. Analyses of the recrystallized erlotinib HCl and fulvestrant were examined by SEM, XRD and DSC. Erlotinib HCl was recrystallized from its mean particle size of 20 μm to 2 μm with different crystal habits. Different polymorphs of erlotinib HCl were obtained and confirmed from the XRD and DSC results. The prior art polymorph form A of erlotinib HCl showed enhanced dissolution rate by 3.6 times to its original polymorph form B. Significant particle size reduction was also obtained for fulvestrant. The mean particle size was reduced from its original value of 22 μm to 2 μm with much narrower particle size distribution. The cross-interaction effect between the operating temperature and pressure observed in the SAS treatment of fulvestrant was verified by the method of calculated mixture critical point (MCP). The micronized fulvestrant particles showed consistent polymorph as the original API, but with different crystal habits. It is confirmed that the SAS method is applicable for controlling the crystal properties of two APIs, erlotinib HCl and fulvestrant, which require rigorous control of physical characteristics.     

Characterisation of the properties of size fractions from ten world coals and their chars produced in a drop-tube furnace

A range of coals from different parts of the world was studied to determine if there were any common relationships that could be determined to gain a clearer understanding of the distribution of coal properties within different particle-sizes. The properties examined were proximate analysis, maceral analysis and %Unreactives from image analysis. Each fraction was also pyrolysed in a drop-tube furnace at 1300°C, 1 vol% oxygen and a residence time of 200 ms and the resulting chars analysed for morphology using image analysis. There were substantial variations between the particle-size distributions of the different coal samples even though they were ground to the same specification for trials on a combustion rig. Ash distributions showed in all cases that the smallest particle size (−38 μm) had either the highest ash level or was very close to it. However, the trends in ash level for increasing particle size showed variations between coals with some coals showing increases in ash towards the larger particles. Fusinite content did not necessarily concentrate in the smallest size fraction, however, liptinite content did increase with particle size. %Unreactives generally increases with particle size and is related to char morphology through an empirical parameter, the ACA [5]. In addition the ACA [5] parameter showed the effect of both particle size and %Unreactives on char morphology and clearly showed the significant influence of particle size on burnout. A parameter such as this could, therefore, be used in burn-out models and further correlated with %Unreactives and particle size.     

A case study on suspended particles in a natural gas urban transmission and distribution network

Suspended particles in the natural gas transmission and distribution network of the city of Kerman, Iran were investigated. Particle concentration and size distribution were measured in different locations of the natural gas pipeline network. Particle samplings were carried out in two seasons: summer, when there is the lowest consumption, and winter, when there is the highest consumption of natural gas. Additional particle characterization was carried out by scanning electron microscopy coupled with energy dispersion X-ray (SEM/EDX) and X-ray diffraction(XRD) analyses. Particle concentration was found to be significantly higher in winter as compared to summer. The range of particle concentrations in summer was from 0.12 mg/Nm³ at the end of the pipeline to 4.7 mg/Nm³ at the network entrance, and from 0.30 mg/Nm³ to 22.1 mg/Nm³ in winter. Particle size distribution showed a higher frequency of smaller particles in winter than in summer. Larger particles were more likely to exist at the network entrance as compared to the exit. The average particle size ranged from 181 μm at the network end to 253 μm at the entrance in summer, and from 74 μm to 209 μm in winter. Particle characterization confirmed the presence of corrosion products in the suspended particles.     

Computational modelling of the impact of particle size to the heat transfer coefficient between biomass particles and a fluidised bed

The fluid-particle interaction and the impact of different heat transfer conditions on pyrolysis of biomass inside a 150 g/h fluidised bed reactor are modelled. Two different size biomass particles (350 μm and 550 μm in diameter) are injected into the fluidised bed. The different biomass particle sizes result in different heat transfer conditions. This is due to the fact that the 350 μm diameter particle is smaller than the sand particles of the reactor (440 μm), while the 550 μm one is larger. The bed-to-particle heat transfer for both cases is calculated according to the literature. Conductive heat transfer is assumed for the larger biomass particle (550 μm) inside the bed, while biomass-sand contacts for the smaller biomass particle (350 μm) were considered unimportant. The Eulerian approach is used to model the bubbling behaviour of the sand, which is treated as a continuum. Biomass reaction kinetics is modelled according to the literature using a two-stage, semi-global model which takes into account secondary reactions. The particle motion inside the reactor is computed using drag laws, dependent on the local volume fraction of each phase. FLUENT 6.2 has been used as the modelling framework of the simulations with the whole pyrolysis model incorporated in the form of User Defined Function (UDF).